JPH0662707B2 - Process for producing polymer containing α-halogenoisopropenylcumene unit - Google Patents
Process for producing polymer containing α-halogenoisopropenylcumene unitInfo
- Publication number
- JPH0662707B2 JPH0662707B2 JP2645985A JP2645985A JPH0662707B2 JP H0662707 B2 JPH0662707 B2 JP H0662707B2 JP 2645985 A JP2645985 A JP 2645985A JP 2645985 A JP2645985 A JP 2645985A JP H0662707 B2 JPH0662707 B2 JP H0662707B2
- Authority
- JP
- Japan
- Prior art keywords
- unit
- halogenoisopropenylcumene
- copolymer
- diisopropenylbenzene
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は反応性に富むα−ハロゲノクメン残基を含有す
る重合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a polymer containing a highly reactive α-halogenocene residue.
反応性の官能基を有するポリスチレン誘導体としては各
種のものがあるが、中でもクロルメチルスチレン単位を
含有する重合体はその反応活性に優れていることから反
応性重合体として極めて有用である。There are various polystyrene derivatives having a reactive functional group, and among them, a polymer containing a chloromethylstyrene unit is extremely useful as a reactive polymer because of its excellent reaction activity.
上記クロルメチルスチレン単位を含有する重合体は、通
常ポリスチレン誘導体にクロルメチル化剤を反応させて
製造されているが、クロルメチル化剤の毒性、反応の収
率及びクロルメチルスチレン単位の量比の制御性等に問
題がある。そのため上記問題のない方法でクロルメチル
スチレン単位含有重合体と同様の反応性を有する重合体
を製造する方法の開発が望まれている。The polymer containing the above chloromethylstyrene unit is usually produced by reacting a polystyrene derivative with a chloromethylating agent, but the toxicity of the chloromethylating agent, the reaction yield and the controllability of the amount ratio of the chloromethylstyrene unit are controlled. Etc. has a problem. Therefore, it is desired to develop a method for producing a polymer having the same reactivity as that of the chloromethylstyrene unit-containing polymer without the above problem.
本発明者らは、上記問題点を解決するため鋭意検討し、
遂に本発明を完成するに到つた。The present inventors have conducted diligent studies to solve the above problems,
Finally, the present invention has been completed.
すなわち、本発明はスチレンおよび／またはその誘導体
とジイソプロペニルベンゼンをラジカル重合して得たイ
ソプロペニル残基含有共重合体にハロゲン化水素を付加
反応させることを特徴とする一般式 （式中、Ｘはハロゲン原子である。） で表わされるα−ハロゲノイソプロペニルクメン単位含
有重合体の製造方法である。That is, the present invention is characterized by adding hydrogen halide to an isopropenyl residue-containing copolymer obtained by radical polymerization of styrene and / or a derivative thereof and diisopropenylbenzene. (In the formula, X is a halogen atom.) A method for producing an α-halogenoisopropenylcumene unit-containing polymer represented by:
本発明においては、スチレンおよび／またはその誘導体
とジイソプロペニルベンゼンをラジラカル共重合させて
得たイソプロペニル残基を含有する重合体を用いる。In the present invention, a polymer containing an isopropenyl residue obtained by radial copolymerizing styrene and / or a derivative thereof and diisopropenylbenzene is used.
ここにおいてスチレンの誘導体とはベンゼン環置換誘導
体であり、ｐ−、ｍ−、ｏ−メチルスチレン、ｐ−、ｍ
−、ｏ−メトキシスチレン、ｐ−、ｍ−、ｏ−クロルス
チレンなどのアルキル基、アルコキシ基、ハロゲン等で
ベンゼン環の１〜３個の水素が置換されたものが例示で
きる。Here, the styrene derivative is a benzene ring-substituted derivative, and includes p-, m-, o-methylstyrene, p-, and m.
Examples thereof include alkyl groups such as-, o-methoxystyrene, p-, m-, and o-chlorostyrene, alkoxy groups, halogens and the like in which 1 to 3 hydrogens on the benzene ring are substituted.
ジイソプロペニルベンゼンとしては、1,3−ジイソプロ
ペニルベンゼン及び1,4−ジイソプロペニルベンゼンで
あり、これらは混合物も使用できる。Examples of diisopropenylbenzene include 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene, and a mixture thereof can be used.
なお、ラジカル共重合時のジイソプロペニルベンゼンの
使用量は、重合体中のイソプロペニル残基所望量により
変わるが、通常モノマー中で１〜８０モル％、好ましく
は５〜５０モル％である。The amount of diisopropenylbenzene used during radical copolymerization varies depending on the desired amount of isopropenyl residue in the polymer, but is usually 1 to 80 mol%, preferably 5 to 50 mol% in the monomer.
また、必要に応じスチレンおよび／またはその誘導体と
ジイソプロペニルベンゼンと共に他の共重合性単量体を
共重合させることができる。If necessary, other copolymerizable monomers can be copolymerized with styrene and / or its derivative and diisopropenylbenzene.
本発明に用いる重合体は、上記スチレンおよび／または
その誘導体とジイソプロペニルベンゼンを、必要に応じ
他の共重合性単量体と共に、通常、好ましくは溶媒の存
在下に、ベンゾイルパーオキサイド、ｔ−ブチルヒドロ
パーオキサイドなどの有機過酸化物、アゾビスブチロニ
トリルなどのアゾビスニトリル類、過硫酸塩、過酸化水
素などの無機過酸化物等のラジカル発生剤（重合開始
剤）により共重合させる。なお、この共重合は重合開始
剤を用いることなく熱重合によつてもかまわない。The polymer used in the present invention comprises the above-mentioned styrene and / or its derivative and diisopropenylbenzene, if necessary together with other copolymerizable monomers, usually, preferably in the presence of a solvent, benzoyl peroxide, t -Copolymerization with radical generators (polymerization initiators) such as organic peroxides such as butylhydroperoxide, azobisnitriles such as azobisbutyronitrile, persulfates, inorganic peroxides such as hydrogen peroxide Let Note that this copolymerization may be performed by thermal polymerization without using a polymerization initiator.
ここにおいて、用いる重合開始剤として金属分を含まな
いものが、得られる重合体にハロゲン化水素を付加させ
て得られるα−ハロゲノイソプロペニルクメン単位含有
重合体に金属分が入らないので好ましい。As the polymerization initiator to be used here, those not containing a metal component are preferable, since the metal component does not enter the α-halogenoisopropenylcumene unit-containing polymer obtained by adding hydrogen halide to the obtained polymer.
重合開始剤の使用量は、モノマー組成、目的とする重合
度等により適宜決定すればよい。The amount of the polymerization initiator used may be appropriately determined depending on the monomer composition, the desired degree of polymerization and the like.
また、反応温度は、ラジカル発生の種類により異なり特
定できないが、重合開始剤を使用する場合には−５０〜
１５０℃程度、通常は常温〜100℃程度である。Further, the reaction temperature differs depending on the type of radical generation and cannot be specified, but when a polymerization initiator is used, it is -50 to
It is about 150 ° C., usually room temperature to 100 ° C.
本発明においては、上述の操作で得られるスチレンおよ
び／またはその誘導体とジイソプロペニルベンゼンの共
重合体にハロゲン化水素の付加反応が行なわれる。共重
合体中のイソプロペニル基は反応性に富むので、上記共
重合体をハロゲン化炭素などの良溶媒に溶解し、次いで
該溶液中にハロゲン化水素ガスを必要に応じ窒素などの
不活性ガスで希釈して、単に導入するだけでほぼ定量的
に反応が進行する。In the present invention, the hydrogen halide addition reaction is carried out on the copolymer of styrene and / or its derivative obtained by the above-mentioned operation and diisopropenylbenzene. Since the isopropenyl group in the copolymer is highly reactive, the above copolymer is dissolved in a good solvent such as carbon halide, and then hydrogen halide gas is added to the solution as necessary with an inert gas such as nitrogen. The reaction proceeds almost quantitatively by simply diluting with.
ここにおいて用いるハロゲン化水素としては、塩化水
素、臭化水素、フッ化水素、ヨウ化水素であり、目的に
より適宜選択される。The hydrogen halide used here is hydrogen chloride, hydrogen bromide, hydrogen fluoride or hydrogen iodide, and is appropriately selected depending on the purpose.
以下、実施例により本発明をさらに説明する。 Hereinafter, the present invention will be further described with reference to examples.
実施例１ 内容積３００mlのフラスコにトルエン１６０ml、スチレ
ン３６mlおよび1,3−ジイソプロペニルベンゼン４mlを
入れ窒素置換した後、アゾビスイソブチロニトリル２ｇ
を加え、９０℃に加熱攪拌して５時間反応した。反応混
合液を多量のメタノール中に注ぎ共重合体を沈澱させ
た。沈澱物を過、乾燥して共重合体１５ｇを得た。こ
の共重合体の極限粘度は0.073であつた。Example 1 160 ml of toluene, 36 ml of styrene and 4 ml of 1,3-diisopropenylbenzene were placed in a flask having an inner volume of 300 ml and the atmosphere was replaced with nitrogen, and then 2 g of azobisisobutyronitrile was added.
Was added, and the mixture was heated and stirred at 90 ° C. and reacted for 5 hours. The reaction mixture was poured into a large amount of methanol to precipitate the copolymer. The precipitate was filtered and dried to obtain 15 g of copolymer. The intrinsic viscosity of this copolymer was 0.073.
上記して得た共重合体５ｇをクロロホルム100mlに溶か
し、攪拌している中に塩化水素ガスを１４０ml/minで３
０分間吹き込み、塩化水素を付加させた後クロロホルム
と未反応の塩化水素を除去した。5 g of the copolymer obtained above was dissolved in 100 ml of chloroform, and hydrogen chloride gas was added at 140 ml / min while stirring.
After bubbling for 0 minute to add hydrogen chloride, chloroform and unreacted hydrogen chloride were removed.
得られた重合体は、赤外線吸収スペクトルにおいて、原
料の共重合体にみられたイソプロペニル基に基づく吸収
（１６３０cm-1）が消失していること、核磁気共鳴スペ
クトルにおいてα−ハロゲノイソプロピル基が定量的に
生成していること等から、α−ハロゲノイソプロペニル
クメン単位を4.8モル％含有する共重合体であつた。な
お、この共重合体の極限粘度は0.078であつた。In the infrared absorption spectrum of the obtained polymer, the absorption (1630 cm −1 ) based on the isopropenyl group found in the copolymer as the raw material disappeared, and the α-halogenoisopropyl group showed in the nuclear magnetic resonance spectrum. Since it was produced quantitatively, it was a copolymer containing 4.8 mol% of α-halogenoisopropenylcumene unit. The intrinsic viscosity of this copolymer was 0.078.
また、このα−ハロゲノイソプロペニルクメン単位含有
共重合体は、３００Ｗ水銀灯で１０cmの距離から照射す
ると３時間後にはクロロホルムに不溶であつた。The α-halogenoisopropenylcumene unit-containing copolymer was insoluble in chloroform after 3 hours when irradiated with a 300 W mercury lamp from a distance of 10 cm.
実施例２ 実施例１においてスチレンと1,3−ジイソプロペニルベ
ンゼンの使用量を夫々３２m1、８mlに変えるほかは実施
例１と同様にしてイソプロペニル残基含有共重合体12.8
ｇを得た。なお、この共重合体の極限粘度は0.080であ
つた。Example 2 A copolymer containing an isopropenyl residue 12.8 was prepared in the same manner as in Example 1 except that the amounts of styrene and 1,3-diisopropenylbenzene used in Example 1 were changed to 32 ml and 8 ml, respectively.
g was obtained. The intrinsic viscosity of this copolymer was 0.080.
さらに実施例１と同様にしてα−ハロゲノイソプロペニ
ルクメン単位含有共重合体（極限粘度0.068）を得た。
なお、赤外線吸収スペクトルよりイソプロペニル基が全
て反応していること及び核磁気共鳴スペクトルよりα−
ハロゲノイソプロペニルクメン単位が8.5モル％含有さ
れていることを確認した。Further, in the same manner as in Example 1, an α-halogenoisopropenylcumene unit-containing copolymer (intrinsic viscosity 0.068) was obtained.
It should be noted that from the infrared absorption spectrum, all the isopropenyl groups have reacted and from the nuclear magnetic resonance spectrum, α-
It was confirmed that the halogenoisopropenylcumene unit was contained in an amount of 8.5 mol%.
実施例３ 実施例１においてスチレンに代えてｐ−メチルスチレン
を用いるほかは実施例１と同様にして、α−ハロゲノイ
ソプロペニルクメン単位含有共重合体（α−ハロゲノイ
ソプロペニルクメン単位5.2モル％、極限粘度0.065）を
得た。Example 3 An α-halogenoisopropenylcumene unit-containing copolymer (α-halogenoisopropenylcumene unit 5.2 mol%, was prepared in the same manner as in Example 1 except that p-methylstyrene was used instead of styrene in Example 1. An intrinsic viscosity of 0.065) was obtained.
実施例４ 実施例１においてスチレンに代えてｐ−メトキシスチレ
ンを用いるほかは実施例１と同様にしてα−ハロゲノイ
ソプロペニルクメン単位含有共重合体（α−ハロゲノイ
ソプロペニルクメン単位5.8モル％、極限粘度0.068）を
得た。Example 4 An α-halogenoisopropenylcumene unit-containing copolymer (α-halogenoisopropenylcumene unit 5.8 mol%, ultimate) was prepared in the same manner as in Example 1 except that p-methoxystyrene was used instead of styrene. A viscosity of 0.068) was obtained.
本発明の方法によつて、α−ハロゲノイソプロペニルク
メン単位を所望の量含有する重合体を簡単に得ることが
可能であり、当該重合体は極めて反応性に富むためレジ
スト用に、あるいはイオン交換樹脂用原料樹脂として使
用可能であり、工業的に極めて意義がある。According to the method of the present invention, it is possible to easily obtain a polymer containing a desired amount of α-halogenoisopropenylcumene unit. Since the polymer is extremely reactive, it can be used for resist or ion exchange. It can be used as a raw material resin for resins and is extremely significant industrially.
Claims (1)
ソプロペニルベンゼンをラジカル共重合して得たイソプ
ロペニル残基含有共重合体にハロゲン化水素を付加反応
させることを特徴とする一般式 （式中、Ｘはハロゲン原子である。） で表わされるα−ハロゲノイソプロペニルクメン単位含
有共重合体の製造方法。1. A general formula characterized by adding hydrogen halide to an isopropenyl residue-containing copolymer obtained by radical copolymerization of styrene and / or its derivative and diisopropenylbenzene. (In the formula, X is a halogen atom.) A method for producing an α-halogenoisopropenylcumene unit-containing copolymer represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2645985A JPH0662707B2 (en) | 1985-02-15 | 1985-02-15 | Process for producing polymer containing α-halogenoisopropenylcumene unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2645985A JPH0662707B2 (en) | 1985-02-15 | 1985-02-15 | Process for producing polymer containing α-halogenoisopropenylcumene unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61188407A JPS61188407A (en) | 1986-08-22 |
| JPH0662707B2 true JPH0662707B2 (en) | 1994-08-17 |
Family
ID=12194089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2645985A Expired - Lifetime JPH0662707B2 (en) | 1985-02-15 | 1985-02-15 | Process for producing polymer containing α-halogenoisopropenylcumene unit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662707B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04250778A (en) * | 1991-01-25 | 1992-09-07 | Victor Co Of Japan Ltd | Vertical contour correction circuit |
-
1985
- 1985-02-15 JP JP2645985A patent/JPH0662707B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61188407A (en) | 1986-08-22 |
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